CN109896714B - Pretreatment method of rubber auxiliary CBS production wastewater - Google Patents
Pretreatment method of rubber auxiliary CBS production wastewater Download PDFInfo
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- CN109896714B CN109896714B CN201910304480.3A CN201910304480A CN109896714B CN 109896714 B CN109896714 B CN 109896714B CN 201910304480 A CN201910304480 A CN 201910304480A CN 109896714 B CN109896714 B CN 109896714B
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Abstract
The invention relates to a pretreatment method of rubber auxiliary CBS production wastewater, belonging to the technical field of industrial wastewater treatment. The pretreatment method of the rubber auxiliary CBS production wastewater comprises the following steps: mixing the mother liquor after reaction with washing water to obtain original wastewater, adding a salting-out agent for salting-out, and separating into a water phase substance and an oil phase substance after salting-out; evaporating the water phase substance to obtain condensate and salt, and then carrying out biochemical treatment on the condensate; rectifying the oil phase substance to obtain a cyclohexylamine recovered substance. Compared with the method for directly evaporating the original wastewater, the method has the advantages that the oil phase is removed by salting out, and then evaporation is carried out, so that the evaporation amount is reduced, the energy consumption during evaporation can be reduced, the process is simpler, the treatment cost is reduced, the separated salt can be recycled during evaporation of the water phase, the salting-out dosage for salting-out is reduced, and the cost is saved.
Description
Technical Field
The invention belongs to the technical field of industrial wastewater treatment, and particularly relates to a pretreatment method of rubber auxiliary CBS production wastewater.
Background
The rubber auxiliary agent CBS, namely N-cyclohexyl-2-benzothiazole sulfonamide, is a highly active post-effect semi-overspeed accelerator, and has the advantages of excellent scorch resistance, safe processing and short vulcanization time. The existing process generally adopts a two-step oxidation method of hydrogen peroxide and sodium hypochlorite, generates a large amount of high-concentration salt-containing organic wastewater in the production process, is difficult to treat, and is severely restricted due to the production and development of the environmental-friendly pressure rubber auxiliary CBS. The wastewater in the production process mainly comes from mother liquor distillation and water washing processes, the salt content and COD concentration of the wastewater are high, the wastewater has color and smell, and meanwhile, the wastewater contains various heterocyclic organic matters, so that the wastewater is difficult to directly treat by methods such as biochemistry and the like.
When the salt-containing wastewater is treated, the mother liquor and washing water are generally mixed and distilled, cyclohexylamine is recovered, aeration is carried out to separate out and settle organic matters such as resin, and then multiple-effect or MVR evaporation desalination is carried out, the COD of the distillate still reaches more than 3000mg/L, and the distillate enters a biochemical system for treatment after pretreatment such as micro-electrolysis.
Other methods for treating the salt-containing wastewater exist in the prior art. The invention patent with application publication number CN102874961A discloses a method for treating rubber vulcanization accelerator rubber auxiliary CBS wastewater, which comprises the following steps: firstly, performing acid-base flocculation on the wastewater, feeding the filtered wastewater into an electrolytic cell filled with micro-electrolysis filler for electrolysis and filtration, adding hydrogen peroxide into the filtered wastewater for Fenton oxidation, performing flocculation, sedimentation and filtration on the oxidized wastewater, and adsorbing the filtered wastewater by using activated carbon and resin in sequence, wherein the removal rate of CODcr reaches more than 98 percent and reaches the discharge standard.
Disclosure of Invention
The invention aims to provide a pretreatment method of rubber auxiliary CBS production wastewater, which has simple process and good treatment effect.
In order to achieve the above purpose, the invention adopts the technical scheme that: the pretreatment method of the rubber auxiliary CBS production wastewater comprises the following steps:
1) mixing the mother liquor after reaction with washing water to obtain original wastewater, adding a salting-out agent for salting-out, and separating into a water phase substance and an oil phase substance after salting-out;
2) evaporating the water phase substance in the step 1) to obtain condensate and salt, and then carrying out biochemical treatment on the condensate;
3) rectifying the oil phase material in the step 1) to obtain a cyclohexylamine recovered material.
Preferably, the salting-out agent in step 1) is a sodium salt or a potassium salt.
Preferably, the sodium salt in the step 1) is one or more of sodium sulfate and sodium chloride, and the potassium salt is one or two of potassium sulfate and potassium chloride.
Preferably, the salting-out agent in step 1) is a sodium salt or a potassium salt.
Preferably, the salting-out agent in step 1) is a sodium salt.
Preferably, the salting-out agent in step 1) is sodium chloride.
Preferably, the salting-out process in step 1) is: after adding a salting-out agent to the original wastewater, stirring the mixture to dissolve the salting-out agent, and then standing the mixture to separate oil from water.
Preferably, the standing time during salting out in the step 1) is 60-240 min.
Preferably, the addition amount of the salting-out agent in the salting-out in the step 1) accounts for 10-40% of the mass of the original wastewater.
Preferably, the evaporation in the step 2) is multi-effect evaporation or MVR evaporation, and COD of the condensate obtained by evaporation is less than 1200 mg/L.
Preferably, the pH of the water phase substance in the step 2) is adjusted to 5-8 before evaporation.
Preferably, when the oil phase material is rectified in the step 3), the tower bottom temperature of the rectifying tower is 98-120 ℃.
The invention has the beneficial effects that:
the pretreatment method of the rubber auxiliary CBS production wastewater comprises the steps of firstly adding a salting-out agent into a mixed solution of mother liquor and washing water, namely original wastewater, for salting out, dividing the mixed solution into an oil phase substance and a water phase substance after salting out, evaporating the water phase substance for desalting to obtain a condensate with COD content suitable for biochemical treatment, and rectifying the oil phase substance by a rectifying tower to recover cyclohexylamine. Compared with the method of directly evaporating the original wastewater, the method has the advantages that the oil phase is removed by salting out and then evaporation is carried out, the evaporation amount is reduced, and the energy consumption during evaporation can be reduced.
According to the pretreatment method for the rubber auxiliary CBS production wastewater, the COD of the condensate after evaporation is less than 1200mg/L, compared with the method that the COD of the distillate after the original wastewater is directly evaporated is more than 3000mg/L, the condensate with the COD less than 1200mg/L can be directly subjected to biochemical reaction, micro-electrolysis and other treatment processes are not needed, the process is simple, and the treatment cost is reduced.
According to the pretreatment method of the rubber auxiliary CBS production wastewater, the salt separated during evaporation of the water phase substance can be recycled and used for next salting-out, the salting-out dosage for salting-out is reduced, and the cost is saved.
According to the pretreatment method of the rubber auxiliary CBS production wastewater, the oil phase substance is subjected to cyclohexylamine recovery through the rectifying tower, the oil phase substance after the water phase is removed, the tower bottom temperature of the rectifying tower is controlled during rectification, the mass percent of the rectified cyclohexylamine can be controlled to be more than 37%, and the cyclohexylamine content is high.
Detailed Description
The present invention will be further described with reference to the following examples.
Example 1
The pretreatment method for the rubber auxiliary CBS production wastewater of the embodiment comprises the following steps:
1) and mixing the mother liquor after reaction with washing water to obtain original wastewater, and taking 1000kg of the original wastewater to obtain the original wastewater with the COD value of 128000 mg/L. Adding 300kg of sodium chloride into the original wastewater, stirring to dissolve the sodium chloride, standing for 60min to separate oil from water, wherein the lower layer is a water phase substance and the upper layer is an oil phase substance, separating the water phase substance at the lower layer by using a sight glass, and pumping the water phase substance into a neutralization tank by using a pump.
2) Adjusting the pH value of the water phase material in the neutralization tank to 7.5, then carrying out multi-effect evaporation on the water phase material by using a multi-effect evaporator, and carrying out multi-effect evaporation according to conventional conditions to obtain condensate with the COD value of 880mg/L, sodium chloride obtained by separation and salt substances in the original wastewater.
3) And rectifying the oil phase substance by using a rectifying tower to obtain a cyclohexylamine recovered substance, wherein the tower bottom temperature of the rectifying tower is 110 ℃, and the tower top temperature of the rectifying tower is 95 ℃ to obtain a distillate in which the cyclohexylamine accounts for 38.0% by mass.
Example 2
The pretreatment method for the rubber auxiliary CBS production wastewater of the embodiment comprises the following steps:
1) and mixing the mother liquor after reaction with washing water to obtain original wastewater, and taking 1000kg of the original wastewater to obtain the original wastewater with the COD value of 136000 mg/L. Adding 250kg of sodium chloride into the original wastewater, stirring to dissolve the sodium chloride, standing for 180min to separate oil and water layers, wherein the lower layer is a water phase substance and the upper layer is an oil phase substance, separating the water phase substance at the lower layer by using a sight glass, and pumping the water phase substance into a neutralization tank by using a pump.
2) Adjusting the pH value of the water phase material in the neutralization tank to 6.0, then carrying out multi-effect evaporation on the water phase material by using a multi-effect evaporator, and carrying out multi-effect evaporation according to conventional conditions to obtain condensate with the COD value of 1160mg/L, sodium chloride obtained by separation and salt substances in the original wastewater.
3) And rectifying the oil phase substance by using a rectifying tower to obtain a cyclohexylamine recovered substance, wherein the tower bottom temperature of the rectifying tower is 108 ℃, the tower top temperature is 97 ℃, and the mass percent of cyclohexylamine in the distillate obtained by rectification is 37.2%.
Example 3
1) And mixing the mother liquor after reaction with washing water to obtain original wastewater, and measuring the COD value of the original wastewater to be 97000mg/L by taking 1000kg of the original wastewater. Adding 200kg of sodium chloride into the original wastewater, stirring to dissolve the sodium chloride, standing for 240min to separate oil from water, wherein the lower layer is a water phase substance and the upper layer is an oil phase substance, separating the water phase substance at the lower layer by using a sight glass, and pumping the water phase substance into a neutralization tank by using a pump.
2) Adjusting the pH value of the water phase material in the neutralization tank to 5.8, then carrying out multi-effect evaporation on the water phase material by using a multi-effect evaporator, and carrying out multi-effect evaporation according to conventional conditions to obtain condensate with the COD value of 1045mg/L, sodium chloride obtained by separation and salt substances in the original wastewater.
3) And rectifying the oil phase substance by using a rectifying tower to obtain a cyclohexylamine recovered substance, wherein the tower bottom temperature of the rectifying tower is 105 ℃, the tower top temperature is 100 ℃, and the mass percent of cyclohexylamine in the effluent liquid obtained by rectifying is 41.6%.
Example 4
1) And mixing the mother liquor after reaction with washing water to obtain original wastewater, and measuring the COD value of the original wastewater to be 146000mg/L by taking 1000kg of the original wastewater. Adding 350kg of sodium chloride into the original wastewater, stirring to dissolve the sodium chloride, standing for 180min to separate oil and water layers, wherein the lower layer is a water phase substance and the upper layer is an oil phase substance, separating the water phase substance at the lower layer by using a sight glass, and pumping the water phase substance into a neutralization tank by using a pump.
2) Adjusting the pH value of the water phase material in the neutralization tank to 7.0, then carrying out multi-effect evaporation on the water phase material by using a multi-effect evaporator, and carrying out multi-effect evaporation according to conventional conditions to obtain condensate with the COD value of 685mg/L, sodium chloride obtained by separation and salt substances in the original wastewater.
3) And rectifying the oil phase substance by using a rectifying tower to obtain a cyclohexylamine recovered substance, wherein the tower bottom temperature of the rectifying tower is 105 ℃, the tower top temperature is 96 ℃, and the mass percent of cyclohexylamine in the effluent liquid obtained by rectification is 43%.
Example 5
1) And (3) mixing the mother liquor after reaction with washing water to obtain original wastewater, and measuring the COD value of the original wastewater to be 123000mg/L by taking 1000kg of the original wastewater. Adding 20kg of sodium sulfate into the original wastewater, stirring to dissolve sodium chloride, standing for 60min to separate oil and water, separating the lower layer from the upper layer, and pumping the lower layer from the water phase by using a sight glass into a neutralization tank.
2) Adjusting the pH value of the water phase material in the neutralization tank to 7.5, then carrying out multi-effect evaporation on the water phase material by using a multi-effect evaporator, and carrying out multi-effect evaporation according to conventional conditions to obtain condensate with the COD value of 830mg/L, sodium sulfate obtained by separation and salt substances in the original wastewater.
3) And rectifying the oil phase substance by using a rectifying tower to obtain a cyclohexylamine recovered substance, wherein the tower bottom temperature of the rectifying tower is 103 ℃, the tower top temperature is 95 ℃, and the mass percent of cyclohexylamine in the effluent liquid obtained by rectification is 39.3%.
Example 6
1) And mixing the mother liquor after reaction with washing water to obtain original wastewater, and taking 1000kg of the original wastewater to obtain the original wastewater with the COD value of 103000 mg/L. Adding 300kg of sodium sulfate into the original wastewater, stirring to dissolve sodium chloride, standing for 80min to separate oil and water, wherein the lower layer is a water phase substance and the upper layer is an oil phase substance, separating the water phase substance at the lower layer by using a sight glass, and pumping the water phase substance into a neutralization tank by using a pump.
2) Adjusting the pH value of the water phase material in the neutralization tank to 7.5, then carrying out multi-effect evaporation on the water phase material by using a multi-effect evaporator, and carrying out multi-effect evaporation according to conventional conditions to obtain condensate with the COD value of 930mg/L, sodium sulfate obtained by separation and salt substances in the original wastewater.
3) And rectifying the oil phase substance by using a rectifying tower to obtain a cyclohexylamine recovered substance, wherein the tower bottom temperature of the rectifying tower is 120 ℃, the tower top temperature is 105 ℃, and the mass percent of cyclohexylamine in effluent liquid obtained by rectifying is 38.9%.
Claims (8)
1. The pretreatment method of the rubber auxiliary CBS production wastewater is characterized by comprising the following steps:
1) mixing the mother liquor after reaction with washing water to obtain original wastewater, adding a salting-out agent for salting-out, and separating into a water phase substance and an oil phase substance after salting-out; the adding amount of the salting-out agent during salting-out accounts for 10-40% of the mass of the original wastewater;
2) evaporating the water phase substance in the step 1) to obtain condensate and salt, and then carrying out biochemical treatment on the condensate;
3) rectifying the oil phase substance in the step 1) to obtain a cyclohexylamine recovered substance, wherein the tower bottom temperature of a rectifying tower is 98-120 ℃.
2. The pretreatment method of wastewater from CBS production as a rubber auxiliary according to claim 1, wherein the pretreatment method comprises the following steps: the salting-out agent in the step 1) is sodium salt or potassium salt.
3. The pretreatment method of wastewater from CBS production as a rubber auxiliary according to claim 2, wherein the pretreatment method comprises the following steps: in the step 1), the sodium salt is one or more of sodium sulfate and sodium chloride, and the potassium salt is one or two of potassium sulfate and potassium chloride.
4. The pretreatment method of wastewater from CBS production as a rubber auxiliary according to claim 2, wherein the pretreatment method comprises the following steps: the salting-out agent in the step 1) is sodium chloride.
5. The pretreatment method of wastewater from CBS production as a rubber auxiliary according to claim 1, wherein the pretreatment method comprises the following steps: the salting-out process in the step 1) is as follows: after adding a salting-out agent to the original wastewater, stirring the mixture to dissolve the salting-out agent, and then standing the mixture to separate oil from water.
6. The pretreatment method of wastewater from CBS production as a rubber auxiliary according to claim 5, wherein the pretreatment method comprises the following steps: the standing time in the salting-out in the step 1) is 60-240 min.
7. The pretreatment method of wastewater from CBS production as a rubber auxiliary according to claim 1, wherein the pretreatment method comprises the following steps: the evaporation in the step 2) is multi-effect evaporation or MVR evaporation, and COD of the condensate obtained by evaporation is less than 1200 mg/L.
8. The pretreatment method for wastewater from CBS production as a rubber auxiliary according to claim 1 or 7, characterized in that: adjusting the pH value to 5-8 before evaporating the water phase substances in the step 2).
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN102432136A (en) * | 2011-09-20 | 2012-05-02 | 科迈化工股份有限公司 | Method for treating wastewater of rubber vulcanization accelerator N-cyclohexyl-2-benzothiazole sulfonamide |
| CN103274898A (en) * | 2013-06-24 | 2013-09-04 | 重庆大学 | Process for recovering distillation waste liquid generated by producing 1,4-butanediol |
| CN107176739A (en) * | 2017-05-27 | 2017-09-19 | 南京工业大学 | A kind of recycling processing method of isobutyrate waste water |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN102432136A (en) * | 2011-09-20 | 2012-05-02 | 科迈化工股份有限公司 | Method for treating wastewater of rubber vulcanization accelerator N-cyclohexyl-2-benzothiazole sulfonamide |
| CN103274898A (en) * | 2013-06-24 | 2013-09-04 | 重庆大学 | Process for recovering distillation waste liquid generated by producing 1,4-butanediol |
| CN107176739A (en) * | 2017-05-27 | 2017-09-19 | 南京工业大学 | A kind of recycling processing method of isobutyrate waste water |
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